Light stabilized hair dye compositions

ABSTRACT

The use of benzylidene camphor to absorb ultraviolet light to stabilize hair dye compositions which contain hair dyeing compounds that are decomposed by exposure to light and cosmetic compositions that contain stabilizing amounts of this compound.

United States Patent [191 Zviak et al.

[451 Oct. 8, 1974 LIGHT STABILIZED'HAIR DYE COMPOSITIONS [75] Inventors:Charles Zviak; Giuliana Ghilardi,

both of Paris, France [73] Assignee: LOreal, Paris, France [22] Filed:Oct. 8, 1971 [211 Appl. No.: 187,874

Related US. Application Data [63] Continuation of Ser. No. 815,501,April ll, 1969,

abandoned.

[52]" us. c1...i.."."..'. s/ 0.1, 8 10, s/19, 424/ IG. 1, 424/DIG. 2,424/47, 424/61, 424/71 [51] 1m. 01 ..A6lk 7/12 [58 Field of Search 8/101[56] References Cited OTHER PUBLICATIONS C mical Abstracts, Vol. 17,Item 2391, 1923.

Comptes Rendas Acadmie Des Sciences, Vol. 176, pp. 45-49, 1923 (I-Ialleret al.).

Beilstein, Vol. VII, 2nd Suppl. p. 346, 1948.

Wells et al., Cosmetics and the Skin, Reinhold Publishing Corp., N.Y-,PP- 39039l, 1964.

Primary ExaminerStanley J. Friedman Assistant Examiner-Vera C. ClarkeAttorney, Agent, or Firm-Cushman, Darby & Cushman 57 ABSTRACT 3 Claims,No Drawings LIGHT STABILIZED I-IAIR D Y E COMPOSITION m This applicationis a continuation of application Ser. No. 815,501 filed Apr. ll, I969,now abandoned.

SUMMARY OF THE INVENTION These compositions may take the form ofsolutions,

emulsions, gels, suspensions, or dispersions, and they are commonlypacked in clear glass or transparent plastic bottles. Hair lacquers, inparticular, are frequently marketed in transparent spray bottles whichpermits the user to see the color of the lacquer.

The composition is thus exposed to the light while being stored or used.

Unfortunately, the dyes are not sufficiently stable when subjected tolight rays. This is particularly true of triphenylmethane derivatives,(such as crystal violet, methyl violet, methyl green) which represent avery valuable range of colors, but have the disadvantage that they arerapidly destroyed by light. There are also a number of other dyes whichare stable at certain concentrations, which are markedly photosensitivewhen highly diluted.

On the other hand, it frequently happens that colorless compositions,such as colorless nail polishes alter and turn yellowish after prolongedexposure to the light.

It follows that these compositions, whether colored or colorless, cannotbe stored for more than a certain length of time, which is usually a fewweeks.

In order to overcome this problem it has been suggested that a substancecapable of filtering out light rays be incorporated in thesecompositions.

However, while the protective filtering substances heretofore used toincrease the length of time for which such compositions may be stored,they do not stabilize them for more than a certain length of time whichvaries with the nature and degree of concentration of the dye, but whichrarely exceeds two months.

Applicants have, however, discovered that the length of time for whichthese cosmetic compositions may be stored can be considerably increasedby incorporating therein a camphor derivative consisting of benzylidenecamphor, or 1, 7, 7-trimethyl-3-benzylidene-2-bicyclo is only slightlysoluble in water, but is readily soluble in such conventional organicsolvents as ethanol, isopropanol, acetone and ethyl acetate. Solutionsof this compound form a very strong absorption bank in the ultravioletrange. J

It is accordingly an object of the present invention to provide a newmethod of protecting cosmetic compositions which are decomposed byexposure to light," which method is essentially characterized by thefact that benzylidene camphor is incorporated in these swaps a In apreferred method of carrying out the process ac- .cording to theinvention, benzylidene camphor is incorporated in these compositions inthe proportion of 0.05

to 2 percent by weight.

It is also an object of the present invention to provide as a newarticle of manufacture a cosmetic composition characterized by the factthat it contains benzylidene camphor.

The compositions according to the invention may be colorless or coloredand take the form of solutions in conventional solvents such as water,the usual alcohols such as ethanol and isopropanol. acetone and ethylacetate, or of emulsions, gels, suspensions or dispersions.

Advantageously, these compositions contain 0.05 to 2 percent be weightof benzylidene camphor.

They may also containany ingredients conventionally included in cosmeticcompositions, such as swelling agents, thickeners, emulsifiers,surface-active agents, bleaches, film-forming" substances, and perEXAMPLE 1 The following colored hair softening lotion'is prepared:

vinylpy'rrolidone/vinyl acetate copolymer sold under the trademarkP.V.P./V.A.S. 630 by General Aniline ethanol q.s.p. methyl violet (Colorlndex.No. 42.535) benzylidene camphor triethanolamine, q.s.p. pH 7water, q.s.p.

[2, 2, l] heptanone, which has the formulas "M This compound. in thepure form, is awhite crystalline powder, having a melting point of7678C, which EXAMPLE 2 The following colored setting lotion is prepared:

vinyl acetate/crotonic acid copolymer vinyl acetate/vinylpyrrolidonecopolymer brilliant rose Cibacete 4 EN" (Color lndex No. 62,015)benzylidene camphor triethanolamine, q.s.p. pH 7 alcohol, q.s.p. 50

water, q .s.p. l

When this solutioni s stored in a clear giass'coiiiame'r and exposed tothe sun it retains its color and coloring power perfectly at the end of6 months. When this solution is not stabilized, its color and coloringpower disappear at the end of 2 weeks, and when stabilized by otherfiltering compounds, they disappear at the end of I 7 weeks.

EXAMPLE 3 The following colored hair lacquer was prepared:

maleic anhydride/methylvinyl ether copolymer sold under the trademarkGantrez AN 3953 by General Aniline triethanolamine, q.s.p. benzylidenecamphor "Orasol Blue BLW" ethanol, q.s.p.

Color Index Solvent Blue 10 CI. 50315) g of this solution wereintroduced into a clear glass aerosol dispenser, in which the followingare added:

Freon ll 47 Freon I2 28 EXAMPLE 4 The following setting lotion isprepared:

resin sold under the trademark PVP K 30 by General ethyl alcohol, q.s.p.

Blue Orasol BLW (Ciba) (Color Index Solvent Blue No. 10 Cl. 503 at aconcentration of 0.05% in a 50 alcoholic solution benzylidene camphorwater, q.s.p.

E WEF A The following setting lotion is prepared:

resin 28.13.10 (Sold by National Starch Co.) 2.5 g aminoethyl propanediol 0.25 g ethyl alcohol, q.s.p. 50 Neolane Rose BA (Ciha) in NZ-solution 0.5-cm, henzylitlene camphor 0.2 g water, q.s.p. 100 em EXAMPLE6 Thefollowing hair softening lotion is prepared:

PVP/VA S 630 (General Aniline) 4 g "Blue sky acid alizarine B"(Francolor) in 0.0571 solution 3 cm henzylidene camphor 0.! g ethylalcohol, q.s.p. 40 water. qsp. 100 cm 9 9-4 NOV mun 100 common? EXAMPLE7 The following setting lotion is prepared:

PVP K 30 (General Aniline) resin 28.13.10 (National Starch Co.)aminoethyl propanol ethyl alcohol, q.s.p.

. FDC Green No. 3 (Color Index No. 42.053) in 0.1% solution benzylidenecamphor water, q.s.p.

EXAMPLE 8 The following shampoo composition is prepared:

Technical (100%) triethanolamine lauryl sulfate monoethanolamide ofcopra oil "isopropylan 33 (Robinson Wagner Co.) carboxymethylcellulosebenzylidene camphor perfume cinnamic alcohol Erioglaucine A or FDC BlueNo. l" (Color index No. 42,090) in an aqueous 1% solution Water. q.s.p.

EXAMPLE 9 The following shampoo composition is prepared:

All these compositions have an excellent stability to light.

In examples 1 and 6 PVP/VA S 630 is a vinylpyrrolidone/vinyl acetatecopolymer that contains percent vinyl pyrrolidone and 30 percent vinylacetate and has a molecular weight of 40,000 to 160,000 and a viscosityin a 25 percent by weight ethanol solution of 100 centipoise. ln example2, the first polymer contained percent vinyl acetate, 10 percentcrotonic acid and had a molecular weight of about 50,000; the secondcopolymer'contained 30 percent vinyl acetate, 70 percent vinylpyrrolidone and had a molecular weightof about 50,000. In example 3,Gantrez AN 3953 has a viscosity of 0.5 centipoise'in 'an aqueoussolution containing 25 percent by weight of said copolymer. In examples4 and 7, PVP K 30" is a polyvinylpyrrolidone copolymer having amolecular weight of about 40,000 and a viscosity of 2.4 centipoise in a5 percent by weight aqueous solution. in examples 5 and 7, resin 28. l3.10 is a copolymer containing 90 percent vinyl acetate, percentcrotonic acid and has a molecular weight of about 50,000. in example 8,lsopropylan 33 is lanoline that is 67 percent transesterified withisopropanol and contains 33 percent free unreacted lanoline.

To more completely identify the hair dyes used in examples 1 to 9 it maybe noted that Neolane Rose BA" is C1 Acid Red 186, color Index No.18,810 having the formula NaOiB O NH:

NHQCHM NaOs brllliant ro se Cibace te 4 BN (C. 1. No. 62,015) has theformula 0 NHa O NH:

nasal Blue BLW(C31f50315lhastheformula FfDC Green No. 31C. 1. N6.121753) hast hFfTifr and FDC Blue Nofl (CTTIINQLJZIWO) hasth formulaoiNHxNa Some of the priorart filtering compounds that were tested andbegan to weaken at the end of days referred to in example 3 are ParsolUltra of Givaddan, Solproter 2 hydro of Firmenich; Domekos WL 334 ofDorily and Tenuvin of CIBA.

Benzylidene camphor and methods of making it are known. For example itis discussed in Beilstein Volume V11-V11, pages 609 and 890, and inVolume VII-2nd supplement, page 346; and Chimie Organic by Gregnard,Volume XV1, pages 209 and 238. One method of making this compound is theHaller method which reacts an aromatic aldehyde with sodium camphor orsodium borneol.

The cosmetic compositions may contain conventional anionic, cationic andanionic emulsifiers, such as magnesium or aluminum stearate, alkylsulphates, such as sodium lauryl sulphate, cetyl alcohol, cetyltrimethyl ammonium bromide, salts of diethylaminoethyloleylamide; Spans,Tweens,-po1yethy1ene glycols, especially those having a molecular weightbetween 200 and 3,000, etc. Many others are listed in Emulsions-Theoryand Practice, Reinhold, Schwartz and Perry (1957). Thickening agentssuch as gelling agents that may be used include for example highconcentrations of emulsifying agents, mixtures of fatty alcohol andalkyl sulphates,-such as lauryl sulphate and cetyl alcohol, ammoniurnsalts of a fatty alcohol-polyoxyethyl sulfate derivatives, such as C 1-l(OC 1-l O1-l, gelatin,.pectin, Agar-Agar gum; polyethylene glycolshaving molecular weights above 100,000, etc.; suspension agents such asethyl ammonium chloride, propyl ammonium sulphate, etc.'and dispersingagents such as lecithine, carboxymethyl cellulose, etc.

Our tests have indicated that a wide variety of hair dyes are stabilizedby benzylidene camphor and all the dyes that we have tested have beenstabilized with this compound. Hair dyes that may be used in the hairdye compositions of this invention include azo hair dyes, such as4,24'6' tetrahydroxy azobenzene, jnitro hair dyes, such as N-methyl4-amino-4-nitro N-B amino ethl-amino propyl amino anthraquinone:triplfinylmeth ane dyes, much as ENQC/ NHgCl, etc.

yl-l-amino benzene, anthraquinon'e hair dyes, such as 7 pyrrolidone andvinyl acetate, vinyl propionat'e, etc; phenyl maleic-methyl anhydridecopolymers, etc.

The shampoo ingredient of the compositions of this invention could beany shampoo compound such as anionic detergents, such as laurylsulfonate, heptadecane benzene sulphonate, fatty acid soaps, Turkey oil,etc.,

alkyl ether sulphates, cationic detergents, such as quaternary ammoniumsalts, such as lauryl trimethyl ammonium sulfate, octadecane pyridiniumsulfate, quaternized amides, nonionic detergents, such as fattyalcoholpolyethers such as lauryl ethoxides, etc., polyethoxy laurylamide, polyethers of ethylene glycol, etc.

The hydratant milk or cream fluid compositions would contain carrierssuch as Vaseline, paraffin oil, lanolin, microcrystalline wax, etc.

The polyethylene glycol distearate used in example 9 had a molecularweight of from 1,000 to 3,000.

The fingernail polish according to the invention may contain, inaddition to one of the dyes given in the foregoing examples,nitrocellulose, acetone, dibutyl phthalate, benzylidene camphor, ethylacetate, butyl acetate, butanol, xylene, and toluene, in proportionswhich may be varied in accordance with principles well known to thoseskilled in the art.

What is claimed is:

1. A hair dye composition comprising a solution in a solvent selectedfrom the group consisting of water, ethanol and isopropanol of a hairdye selected from the group consisting of 4, 2', 4',6'-tetrahydroxyazobenzene, N-methyl-4-amino-4-nitro-N-B-aminOethyl lamino benzene, l-amino propylamino anthraquinone,

S OZNB NHQCHa,

O CHa,

crystal violet, methyl violet and methyl green, present in amountseffective to color hair, said hair dye being susceptible todecomposition by exposure to ultraviolet light and as an effectiveultra-violet light absorbing agent benzylidene camphor having theformula l Y HaC-C-CHS present in amounts of 005-2 percen t by weight ofsaid composition.

2. The hairv dye composition of claim 1 wherein said hair dye isselected from the group consisting of crystal violet, methyl violet andmethyl green.

3. The'hair dye composition of claim 1 which also includes film-formingamounts of a member selected from the group consisting of a. percentvinyl pyrrolidone/30 percent vinyl ace tate copolymer having a molecularweight of 40,000-160,000;

b. percent vinyl acetate/10 percent crotonic acid copolymer having amolecular weight of about 50,000, r

c. 30 percent vinyl acetate/70 percent vinyl pyrrolidone copolymerhaving a molecular weight of about 50,000, and

d. polyvinylpyrrolidone having a molecular weight of about 40,000 and aviscosity of 2.4 centipoises in a 5 weight percent ilqufOlfkS solution.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,840,338 Dated October 8, 1974 I Inventor(s) Charles Zviak and Giglianailardi It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

In the Heading, please add [30] Foreign Application Priority Data March18, 1968 Luxembourg 55702 Signed and sealed this 22nd day of Apri 1 1275 Attest:

C. IZARSIZALL RUTH C. Iii-3 2? Commissioner of Patents Attesting Dfficerand Trademarks

1. A HAIR DYE COMPOSITION COMPRISING A SOLUTION IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER, ETHANOL AND SIOPROPANOL OF A HAIR DYE SELECTED FROM THE CONSISTING OF 4'', 2'', 4'', 6''-TETRAHYDROXYAZOBENZENE, N-METHYL-4-AMINO-4NITRO-N-B-AMINOETHYL-1-AMINO BENZENE, 1-AMINO PROPYLAMINO ANTHRAQUINONE,
 2. The hair dye composition of claim 1 wherein said hair dye is selected from the group consisting of crystal violet, methyl violet and methyl green.
 3. The hair dye composition of claim 1 which also includes film-forming amounts of a member selected from the group consisting of a. 70 percent vinyl pyrrolidone/30 percent vinyl acetate copolymer having a molecular weight of 40,000-160,000, b. 90 percent vinyl acetate/10 percent crotonic acid copolymer having a molecular weight of about 50,000, c. 30 percent vinyl acetate/70 percent vinyl pyrrolidone copolymer having a molecular weight of about 50,000, and d. polyvinylpyrrolidone having a molecular weight of about 40, 000 and a viscosity of 2.4 centipoises in a 5 weight percent aqueous solution. 